Chemical Papers

https://doi.org/10.1007/s11696-018-0387-9

ORIGINAL PAPER

Synthesis and application of a novel magnetic nanosorbent

for determination of trace Cd(II), Ni(II), Pb(II), and Zn(II)
in environmental samples
Zohreh Dahaghin1 · Hassan Zavvar Mousavi1 · Ehsan Mirparizi2 · Parand Haghighat1

Received: 24 August 2017 / Accepted: 8 January 2018

© Institute of Chemistry, Slovak Academy of Sciences 2018

Abstract
In this work for the first time, F
­ e3O4@SiO2 core–shell nanoparticles functionalized with isatin groups as a magnetic nano-
sorbent was applied for the simultaneous extraction of trace amounts of cadmium(II), nickel(II), lead(II), and zinc(II). The
characterization of this nanosorbent was studied using Fourier transform infrared spectroscopy, scanning electron microscopy,
energy-dispersive X-ray spectrometry, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis.
The effect of several factors such as pH, amount of sorbent, extraction time, type and volume of the eluent, sample volume,
sorption capacity, and potentially interfering ions was investigated. In the selected conditions, it was observed that the limits
of detection were 0.11 ng mL−1 for Cd(II), 0.28 ng mL−1 for Ni(II), 0.47 ng mL−1 for Pb(II), and 0.21 ng mL−1 for Zn(II),
and the maximum sorption capacity of this suggested magnetic nanosorbent was 120, 112, 100, and 100 mg g−1 for Cd(II),
Ni(II), Pb(II), and Zn(II), respectively. Also, the precision of the method (RSD%) for ten replicate measurements was found
2.5, 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. Finally, the suggested procedure was applied
for determination of cadmium(II), nickel(II), lead(II), and zinc(II) at trace levels in different water and agricultural products
with satisfactory results.

Keywords Magnetic nanosorbent · Isatin · Cadmium(II) · Nickel(II) · Lead(II) · Zinc(II)

Introduction metallic materials in natural source water was enhanced as a

One of the main problems in environmental pollutants is
heavy metal ions, which have toxic effects on the human
health and life in aquatic systems. Therefore, one of the
greatest interested subjects by analytical chemists is deter-
mining the trace amounts of heavy metals and this is one
of the important subjects in analytical chemistry (Zhang
et al. 1999). The trace amounts of heavy metals are the most
important contaminants in the source water. The presence of
Electronic supplementary material The online version of this
article (http​s://doi.org/10.1007​/s116​96-018-0387​-9) contains
supplementary material, which is available to authorized users.
* Hassan Zavvar Mousavi
hzmousavi@semnan.ac.ir
1
Department of Chemistry, Semnan University,
Semnan 35131‑1911, Iran
2
Young Researchers and Elite Club, Sirjan Branch, Islamic
Azad University, Sirjan, Iran
result of growing the application of heavy metals in indus-
tries and causes several environmental problems (Tangjuank
et al. 2009). Recent years, nanoparticle materials, especially
magnetic nanoparticles have aroused a great deal of atten-
tion in analytical chemistry as the sorbents (Ghaemi and
Absalan 2014; Faraji et al. 2010; Bagheri et al. 2012a).
In contrast, iron oxide nanoparticles due to the important
properties such as the high surface area to volume, nano-
size range and super-magnetism are suitable particles and
in water treatments due to these properties are highly desir-
able (Pan et al. 2010; Laurent et al. 2008). Silica is one of
the most ideal compositions to be used as a shell. The silica
shell protects ­Fe3O4 NPs in acidic medium which is neces-
sary for elution of most metal ions. Also, silica surface with
silanol groups can react with silane coupling to conjugate
with a variety of different ligands (Tadjarodi et al. 2015). A
number of preconcentration methods for preconcentration
and detection of trace metal amounts have gained attention
nowadays, including solvent-assisted dispersive solid-phase
extraction (Behbahani et al. 2015), solid-phase extraction

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Vol.:(0123456789)

(SPE) (Marwani et al. 2015), magnetic solid-phase extrac-
tion (MSPE) (Bagheri et al. 2012b; Zhao et al. 2016), elec-
trochemical deposition (El Aroui et al. 2014), and membrane
separation (Sanaeepur et al. 2016). Isatin (Isa) is chemically
immobilized on different solid supports such as chelating
resin, bentonite, and silica nanoparticles to form various
solid absorbents, where it has been shown to greatly enhance
the removal of heavy metal ions from aqueous solutions.
Isatin is a kind of strong bidentate chelating agent and has
active functional groups containing N, and S, which act as
the chelation with metal cations.
In the current research, for the first time, ­Fe3O4@SiO2
core–shell nanosorbent was modified with isatin (­ Fe3O4@
SiO2@Isa) and used as a novel magnetic solid-phase sorbent
for removal and preconcentration of cadmium(II), nickel(II),
lead(II), and zinc(II) ions, and flame atomic absorption spec-
trometry (AAS) was chosen for monitoring the concentra-
tion of these target ions. The modified magnetic nanosorbent
was synthesized by a simple reaction and characterized by
FT-IR, SEM, EDS, XRD, VSM and TGA. The sorbent was
then used to determine Cd(II), Ni(II), Pb(II), and Zn(II) ions
in different water and agricultural products and the obtained
results were good.
Experimental
Reagents and materials
All reagents used in this study (NaOH, N ­ H3, HCl, ­HNO3,
­H2SO4, isatine, 3-aminopropyltriethoxysilane (APTES),
Cd(NO3)2, Ni(NO3)2, Pb(NO3)2, Zn(NO3)2, toluene, etha-
nol) were purchased from Merck (Darmstadt, Germany),
Fluka (Buchs, Switzerland) or Sigma-Aldrich (Steinheim,
Germany) without any further purification. Tetraethoxysi-
lane, ­FeCl3·6H2O, and F­ eSO4·7H2O were used in magnetic
nanoparticles preparation and were purchased from Aldrich.
The stock solution (1000 mg L−1) was readied by dissolv-
ing suitable amounts of Cd(NO3)2, Ni(NO3)2, Pb(NO3)2, and
Zn(NO3)2 in deionized water.
Apparatus
Concentrations of target metal ions were performed with an
Agilent Series AA (model 240 AA) flame atomic absorp-
tion spectrometer (FAAS) equipped with the air-acetylene
burner. The FT-IR spectra (400–4000 cm−1) were recorded
by S, 8400 Shimadzu FT-IR spectrophotometer. A scanning
electron microscopy (SEM) (KYKY, EM 3200) and energy-
dispersive X-ray spectrometry (EDS) (Tescan Mira3, Czech)
were used to analyze the surface morphology. X-ray powder
diffraction (XRD) patterns were performed using a Bruker
D8 Advance (Germany) with the 2θ angle varying between
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Chemical Papers
5° and 90° (λ = 1.5). Thermogravimetric analyses (TGA)
were conducted with a LINSEIS model STS PT 16000 ther-
mal analyzer at a heating rate of 10 °C ­min−1 for the thermal
gravimetric analysis of synthesized nanoparticles.
Preparation of ­Fe3O4@ ­SiO2 core–shell nanosorbent
Magnetic ­Fe3O4 nanoparticles (MNPs) were obtained based
on simple chemical coprecipitation of ­Fe2+ and ­Fe3+ ions
as reported elsewhere (Saraji and Boroujeni 2014). Briefly,
6.1 g of ­FeCl3·6H2O and 4.2 g of ­Fe2SO4·7H2O [Fe(III)/
Fe(II) molar ratio = 2/1] were dissolved in 100 mL distilled
water, and heated at 80 °C for 30 min, then add 10 mL of
ammonia solution (25 w/w%) dropwise until formation of
­Fe3O4 occurred. This system was mixed for 4 h by a mag-
netic stirrer in the nitrogen atmosphere. During the whole
procedure, the temperature of the solution was held at 80 °C.
The product ­(Fe3O4 NPs) was effectively separated in few
seconds by a strong magnet and repeated washing with dis-
tilled water thoroughly, and finally, the nanoparticles were
vacuum-dried at 40 °C for 4 h. Next, the grafting proce-
dure of magnetic particles with silica was accomplished as
follows:
1 g of the prepared ­Fe3O4 NPs were dispersed via ultra-
sonic in a solution of 100 mL deionized water, 25 mL eth-
anol and 1.5 mL ­NH4OH (25%). Then, 3 mL TEOS was
added dropwise to the solution under stirring until the pro-
cess of magnetic particles with silica was accomplished
(Sadeghi and Aboobakri 2012). After 12 h stirring at 40 °C,
with help of the external magnet, the formed ­Fe3O4@SiO2
NPs were collected and washed with deionized water and
ethanol and then dried.
Functionalization of ­Fe3O4@ ­SiO2 core–shell NPs
The procedure for functionalizing F­ e3O4@SiO2 core–shell
NPs was performed in two steps as follows: In the first step,
1.0 g of F ­ e3O4@SiO2 core–shell NPs were ultrasonically
dispersed in 50 mL dried toluene in a three neck round-
bottom flask. Then, 3-aminopropyltriethoxysilane (2.0 mL)
was added to the solution in one portion after stirring for
1 h. The black solid was produced after refluxing under
nitrogen atmosphere for 12 h. Afterward, ­Fe3O4@SiO2@
APTMS core–shell NPs were isolated by the strong mag-
net and washed with water and ethanol several times until
discard any impurities, GO@Fe3O4@APTMS nanoparticles
were dried completely at 50 °C for overnight and were used
in the next step of the experiment. The FT-IR spectrum,
SEM, EDS and TGA analyses were applied to confirm the
synthesis of GO@Fe3O4 functionalized with APTMS (Bagh-
eri et al. 2016).
In the second step, about 1.0 g of the ­Fe3O4@SiO2@
APTMS core–shell NPs was dispersed in 50 mL toluene
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containing 1.0 g of isatin and the reaction mixture was
stirred and refluxed for 24 h in an oil bath at 80 °C in the
presence of nitrogen. Hereafter, the black solid obtained was
successively collected by a strong magnet and washed sev-
eral times with ethanol to remove excess unreacted materi-
als and dried under vacuum at 40 °C overnight (Fig. 1Sa)
(Electronic Supplementary Material, ESM). Then, FT-IR,
SEM, XRD, VSM and TGA were used for characterizing
obtained ­Fe3O4@SiO2@Isa nanosorbent.
Real sample pretreatment
Presence of cadmium(II), nickel(II), lead(II), and zinc(II)
ions in diverse samples such as water and vegetable sam-
ples were determined by the ­Fe3O4@SiO2@Isa nanosorb-
ent. Water samples, including, tap water (Tehran, Iran), and
river water (Zayanderud, Isfahan, Iran) were selected for
evaluating the influence of the synthetic nanocomposite on
the efficiency of the proposed approach, and then were fil-
tered. 50 mL of each sample was adjusted to pH 6, and their
cadmium(II), nickel(II), lead(II), and zinc(II) ions content
were determined by the suggested extraction and precon-
centration method.
Five types of vegetables, including lettuce, broccoli, car-
rot, cucumber and tomato (local supermarket, Tehran) were
selected and 1 g of each was grounded, homogenized and
dried at 80 °C. After fractionating, the homogenized samples
were sieved, the samples were transferred to a beaker and
dissolved in 10 mL of concentrated nitric acid and heated to
90 °C until brown fumes ceased. Subsequent that 10 mL of
30% hydrogen peroxide was added to each sample, heating
was retained until the sample became clear. The dilution
of obtained solution with double distilled water to 100 mL
was carried out in a volumetric flask after filtration (Pirouz
et al. 2015). The recommended procedure was performed at
optimal conditions.
Extraction procedure
For the extraction procedure, the pH of 10 mL aqueous solu-
tion including 0.5 mg L−1 of target ions was set at optimal
pH (the solution pH was adjusted by dilute NaOH or HCl to
desired value). Then, 20 mg of the dried magnetic nanosorb-
ent was added into the solution and the prepared mixture was
stirred for the suitable amount of time for ensuring adequate
interaction between magnetic sorbent and ions. Afterward,
the magnetic sorbent was collected from the solution with
an appropriate magnet and the concentrations of the metal
ions in supernatant were directly determined by FAAS. In
the elution step, 4 mL of 2 mol L−1 HCl was used to elute
the metal ions adsorbed on the sorbent. For this purpose, the
mixture of sorbent and eluent was stirred for 5 min and then
again exposed on the strong external magnet until obtaining
the clear solution of eluent. Finally, the amount of analyte in
eluent was determined by its injection into FAAS.
It should be noted that the percentage of extraction for
the employed samples was obtained using the following
equation:
%Extraction = Ca −Cb ∕Ca × 100,
where Ca and Cb are initial and final concentrations of each
ion in the solution, respectively (Fig. 1Sb).
Results and discussion
Sorbent characterization
FT-IR spectrum of ­Fe3O4 was recorded using the KBr pellet
method. The advent of the absorption peaks at 582 cm−1 is
ascribed to Fe–O stretching and the band at 3435 cm−1 is due
to the intramolecular hydrogen bonding. The presented find-
ings confirm that the synthesis of ­Fe3O4 NPs was performed
successfully. For the ­Fe3O4@SiO2 nanoparticles, the peaks
at 1089 cm−1 (Si–O–Si) and 798 cm−1 (Fe–O–Si) attributed
that ­SiO2 was successfully coated on the surfaces of ­Fe3O4
nanoparticles.
For ­Fe3O4@SiO2@APTMS, the absorption peak in the
area of 1398 represents a Si–C group in the magnetic nano-
composite structure and the adsorption peak at 2900 cm−1
(C–H) confirmed the existence of APTMS on the surface
of ­Fe3O4@SiO2 NPs. In FT-IR spectrum of F ­ e3O4@SiO2@
Isa nanocomposites, the absorption bands at 1400 and
1618 cm−1 areas represented the vibrational frequency of
C=C and C=N band in ­Fe3O4@SiO2@Isa, respectively.
These observations indicate the modification of F ­ e 3O 4@
SiO2 with Isa group.
SEM and EDS characterization
The morphology of ­Fe3O4@SiO2 and ­Fe3O4@SiO2 nano-
composite functionalized with isatin group was studied using
SEM for showing the structure of the synthesized nanosorb-
ents. Our literature survey at this stage revealed that accord-
ing to SEM patterns shown in Fig. 1a, b reveal the obvious
growth of nanocomposite particle size in ­Fe3O4@SiO2@Isa
nanocomposite. EDS spectra taken from the F ­ e3O4@SiO2@
APTMS nanocomposite are presented in Fig. 2S.
X‑ray characterization
Figure 3S shows XRD patterns of ­Fe3O4@SiO2 nanocom-
posite and ­Fe3O4@SiO2@Isa nanocomposite after reaction
of magnetic ­Fe3O4@SiO2 with isatin group. Different peaks
at 2θ = 30.1, 35.5, 43.2, 57.1 and 62.7 and the broad peak at
2θ = 20–30 ­(SiO2 group) in Fig. 3S showed that the structure
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Fig. 1  The SEM image of a ­Fe3O4@SiO2 b ­Fe3O4@SiO2@Isa nanocomposite

of ­Fe3O4@SiO2 nanoparticles remained intact after coating

with Isa groups and any changes and decomposition occur-
ring in the structure of ­Fe3O4@SiO2 after modification. The
low-angle X-ray diffraction pattern of F ­ e3O4@SiO2@Isa
showed decrease in intensity in peaks in comparison with
unfunctionalized ­Fe3O4@SiO2. The average crystallite size
of the ­Fe3O4@SiO2@Isa NPs was estimated from the XRD
pattern using the Scherrer formula:
D = k𝜆∕cos𝜃,
where D is average crystallite size, λ is the X-ray wave-
length, β is the full-width at half maximum (FWHM) and θ
is the diffraction angle. Here, λ = 1.54 Å is chosen for X-ray
wavelength. Thus, the crystallite size of F ­ e3O4@SiO2 NPs
Fig. 2  The TGA curves of ­
Fe3O4@SiO2@APTMS and F
­e3O4@
and ­Fe3O4@SiO2@Isa NPs were computed from the XRD SiO2@Isa nanocomposites
pattern and found to be about 40 and 50 nm.

Thermogravimetric analysis

TGA analysis of F­ e3O4@SiO2@APTMS and F ­ e3O4@SiO2@

Isa nanocomposites are shown in Fig. 2. According to the
TGA analysis, these nanocomposites are stable up to 600 °C.
The weight losses occurred at 250 °C is due to the loss of
residual water and pyrolysis of oxygen-containing groups
in the surface of nanosorbents. Comparing ­Fe3O4@SiO2@
APTMS and ­Fe3O4@SiO2@Isa curves, the difference in
reduction in weight of these nanocomposites (weight loss
about 30 and 60% for ­Fe3O4@SiO2@APTMS and ­Fe3O4@
SiO2@Isa, respectively) indicates the presence of isatin
group in the nanocomposite.

VSM characterization

Figure 3 shows the magnetization curve of the F ­ e 3O 4@

SiO2@Isa nanocomposites. The saturation magnetization Fig. 3  Magnetization curves of F
­ e3O4@SiO2@Isa nanocomposites at
of the nanocomposite was found to be equal to 15 emu g−1. 300 K

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Optimization of extraction conditions
Effect of pH
To investigate the effect of pH on the extraction recovery,
10 mL of different aqueous sample solutions containing
specified amount of analytes (0.5 mg L−1 of Cd(II), Ni(II),
Pb(II), and Zn(II) ions) was studied in the pH range from 2
to 9. The pH of solutions was set using hydrochloric acid or
sodium hydroxide solutions. As can be observed in Fig. 4S,
the suitable recoveries of target metal ions occurred at pH
6. At alkaline pH, analyte ions convert to M ­ n+(OH)n and
produce hydroxide forms. Thus, they lose their tendency to
form complexes with amine and oxygen groups of magnetic
nanosorbent and the efficiency decreases.
Effect of nanosorbent amounts
For achieving the highest quantitative efficiency for extract-
ing Cd(II), Ni(II), Pb(II), and Zn(II) ions, the optimal
amount of F ­ e3O4@SiO2@Isa nanocomposites was obtained.
Thus, varying amounts of nanocomposite ranging from 5
to 30 mg were tested. The illustrated outcomes in Fig. 5S
indicated by increasing amounts of F ­ e 3O 4@SiO 2@Isa
nanocomposite up to 20 mg and the extraction efficiency
increased in response to the increase of surface area. There-
fore, the subsequent studies were performed using 20 mg of
nanocomposite to get a satisfactory result. The extraction
recovery was nearly constant with using higher amounts of
the sorbent.
Effect of sorption time
Different time periods (2, 4, 5, 8 and 10 min) for Cd(II),
Ni(II), Pb(II), and Zn(II) ions sorption on the magnetic
­Fe3O4@SiO2@Isa nanocomposite were tested. For this step,
20 mg ­Fe3O4@SiO2@Isa was added to 10 mL of sample
solutions (0.5 mg L−1 of target ions) at optimal pH, and
the mixture was shaken for various ranges of time periods.
Based on obtaining outcomes in Fig. 6S, for obtaining the
maximum yield, 5 min is enough for extracting the analytes
from solution quantitatively, and this time was selected as
the optimum sorption time.
Elution condition
In the current study, several types of eluents (HCl, H
­ NO3,
­H2SO4, NaOH, and ­NH3) were selected for elution of Cd(II),
Ni(II), Pb(II), and Zn(II) ions from magnetic ­Fe3O4@SiO2@
Isa nanocomposite and extraction procedure was performed.
The obtained result indicated that the better eluent for Cd(II),
Ni(II), Pb(II), and Zn(II) ions from the sorbent was 3 mL of
2 mol L−1 HCl solution (Fig. 7S). Then, the effect of elution
time on recovery of Cd(II), Ni(II), Pb(II), and Zn(II) ions
was studied in the range of 2–20 min. The results indicated
the suitability of 10 min for a better recovery.
Effect of sample volume
The volume of sample plays an important role in analyzing
real samples and it is effective on the preconcentration factor.
In a condition in which all solutions were adjusted according
to the optimum condition obtained for the suggested tech-
nique, examination of the effect of sample volume param-
eter on quantitative sorption of Cd(II), Ni(II), Pb(II), and
Zn(II) ions was performed using 20 mg of ­Fe3O4@SiO2@Isa
sorbent in various volumes of the sample within the range
of 25–1000 mL containing 1 mg of target ions. According
to the results given in Fig. 4, the recovery of all ions on
the ­Fe3O4@SiO2@Isa nanocomposite was obtained more
than 98% for the sample volumes up to 800 mL, but it was
reduced when dilution was raised up at higher volume. Thus,
800 mL of the sample volume was chosen for the proposed
extraction method and the preconcentration factor (PF) for
synthetic magnetic nanocomposite was calculated to be 266
when 3 mL of elution was used.
Effect of potentially interfering ions
To assess the effect of potentially interfering ions,
several common anions and cations with different
Fig. 4  Effect of sample volume on recovery of Cd(II), Ni(II), Pb(II),
and Zn(II) ions on F­ e3O4@SiO2@Isa nanocomposite
13

concentrations were added to 100 mL of the solution con-
taining 0.003 mg L−1 of cadmium(II), nickel(II), lead(II),
and, zinc(II) (Table 1S). The reported tolerance limit was
herein defined as the ion concentration producing a relative
error ≤ ± 5%. The results showed (Table 1S) this technique
could be suggested for determination of these heavy metal
ions in samples with a complicated matrix with excellent
selectivity.
Maximum adsorption capacity study
The total amount of every analyte sorbed per gram of
the magnetic sorbent is specified as the highest sorption
capacity of the sorbent. To determine this parameter, the
batch MSPE procedure was investigated using an aqueous
solution containing 50 mg L−1 of Cd(II), Ni(II), Pb(II),
and Zn(II) ions, and it was calculated by determining the
difference between the concentration of analyte in the
solution before and after extraction using FAAS. This
parameter was calculated using the following equation:
[ ]
Q = (C0 − CA ) × V ∕m,
where Q, C0, CA, V and m are the amount of metal ions
sorbed onto the unit, amount of the composites (mg g−1), ini-
tial concentration (mg L−1) of each ion, final concentrations
(mg L−1) of each ion, the volume of the aqueous phase (L),
and the weight of the magnetic nanosorbent (g), respectively.
The sorption capacity of magnetic ­Fe3O4@SiO2@Isa nano-
composite was calculated 120, 112,100, and 100 mg g−1
for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. The
sorption capacity of magnetic ­Fe3O4@SiO2 nanocompos-
ite was calculated 50, 80, 37, and 44 mg g−1 for Cd(II),
Ni(II), Pb(II), and Zn(II) ions, respectively, that depicts bet-
ter absorption by ­Fe3O4@SiO2@Isa nanocomposite. Also,
under the chosen conditions, it was observed that ­Fe3O4@
SiO2@Isa nanosorbent can be applied six times without sig-
nificant considerable loss in their sorption capacity.
Analytical performance of method
For this ­F e 3 O 4 @SiO 2 @Isa nanocomposite linearity
was within the range of 0.2–50 ng mL−1 for cadmium,
0.5–120 ng mL−1 for nickel, 1–200 ng mL−1 for lead, and
0.1–90 ng mL−1 for zinc in the initial solution. The cor-
relation of determination (r2) was 0.9966 for Cd(II) and
0.9985 for Ni(II), 0.9985 for Pb(II), and 0.9987 for Zn(II)
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ions. The LOD was calculated based on three times of
blank signal (six replicate blank measurements) divided by
the slope of the calibration curve ­(3Sb/m) and it was 0.11,
0.28, 0.47, and 0.21 ng mL −1 for Cd(II), Ni(II), Pb(II),
and Zn(II), respectively. The relative standard deviation
(RSD%) was measured for a standard solution containing
specific amount of these ions (n = 10). This value was 2.5,
2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II)
ions, respectively.
Determination of Cd(II), Ni(II), Pb(II), and Zn(II) ions
in various real samples
To evaluate the performance of the synthetic ­F e 3O 4@
SiO2@Isa nanocomposites, the suggested technique was
used to determine Cd(II), Ni(II), Pb(II), and Zn(II) in the
real samples such as water and vegetable samples (let-
tuce, broccoli, carrot, cucumber and tomato), under the
optimum conditions. The recovery percentages relating to
extract analytes from real samples were given in Table 1.
Table 1 show that higher yields are obtained using this
novel nanosorbent.
Comparison of developed method with other
published methods
Table 2 presents the results of comparing the characteris-
tic data of mentioned method with other previous methods
(Kumar et al. 2000; Pourreza et al. 2014; Silva and dos San-
tos Roldan 2009; Ghodsbin et al. 2014; ALOthman et al.
2012). According to the table, the obtained detection limit
using ­Fe3O4@SiO2@Isa nanocomposite is significantly
lower than other approaches. As can be seen, this magnetic
nanocomposite has good preconcentration factor comparing
to other techniques.
Conclusion
Heavy metal pollutants are considered to be a criti-
cal contaminant as they pose harmful health risks and
extraction of heavy metal ions from water solutions is
done using different methods and adsorption processes
(Dahaghin et al. 2017a, b, c). In the current research for
the first time, we introduce a novel magnetic nanosorbent
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Table 1  Analysis of cadmium, nickel, lead and zinc ions in different water and agricultural products
Solid sample Analyte Real sample Added Found Recovery (%) RSD%
(ng mL−1) (ng mL−1) (ng mL−1)

Cucumber Cadmium – 10.00 9.00 90.00 1.00

Nickel 6.73 10.00 16.50 97.70 1.35
Lead 3.11 10.00 13.53 104.20 1.65
Zinc 10.43 10.00 20.22 97.90 1.86
Tomato Cadmium – 10.00 8.87 88.70 1.85
Nickel 8.35 10.00 18.16 98.10 1.81
Lead 6.54 10.00 16.04 95.00 1.30
Zinc 8.76 10.00 18.54 97.80 1.76
Carrot Cadmium 2.12 10.00 11.51 93.90 1.56
Nickel 5.41 10.00 15.24 98.30 2.11
Lead – 10.00 9.90 99.00 1.20
Zinc 10.31 10.00 20.10 97.90 2.10
Lettuce Cadmium – 10.00 9.70 97.00 2.23
Nickel 4.51 10.00 14.32 98.10 2.15
Lead – 10.00 8.72 87.20 1.57
Zinc 9.50 10.00 19.40 99.00 2.32
Broccoli Cadmium – 10.00 10.82 108.2 1.68
Nickel 8.27 10.00 18.18 99.10 2.20
Lead 5.89 10.00 15.45 95.60 1.55
Zinc 8.98 10.00 18.70 97.20 1.56
Sample Analyte Real sample Added Found Recovery (%) RSD%
(ng mL−1) (ng mL−1) (ng mL−1)

Tap (Tehran, Iran) Cadmium – 10.00 9.85 98.50 1.83

Nickel – 10.00 9.90 99.00 1.87
Lead – 10.00 11.65 116.5 2.31
Zinc 4.59 10.00 14.20 96.10 1.38
River water (Zayanderud, Cadmium 2.47 10.00 12.24 97.70 1.72
Isfahan, Iran) Nickel 8.49 10.00 18.10 96.10 1.45
Lead 4.23 10.00 13.58 93.50 2.10
Zinc 9.82 10.00 19.69 98.70 2.13

consisted of ­SiO2, ­Fe3O4 nanoparticles, and isatin group
and applied for rapid and facile separation of trace quanti-
ties of cadmium(II), nickel(II), lead(II), and zinc(II) ions
from various matrices. The characterization of this novel
sorbent was performed using FT-IR, SEM, EDS, XRD,
VSM, and TGA. Low LOD and RSD, and excellent yields
with short extraction times are the main advantages of
this magnetic nanocomposite. Another advantage, due to
the high preconcentration factors of this new developed
method, trace amounts of heavy metals in high-volume
samples can be quantified using this magnetic nanocom-
posite. In conclusion, considering the obtained outcomes,
the suggested new nanocomposite is facile, easy and fast,
and can be used in complex matrices.

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Table 2  Comparison between proposed methods with previous works

Instrument Analytical technique Elements LOD PFa MACb Refs.

(ng mg−1) (mg g−1)

FAAS XAD-2 functionalized with o-aminophenol Cadmium 2.0 50 3.42 Pirouz et al. (2015)
Nickel 7.5 65 3.24
Lead 25.0 40 3.32
Zinc – – –
FAAS Nano-TiO2-MBT-FAAS Cadmium 0.12 106 – Pourreza et al. (2014)
Nickel – – –
Lead 1.38 83 –
Zinc – – –
FAAS Cloud point extraction Cadmium 0.74 43 – Sadeghi and Aboobakri (2012)
Nickel – – –
Lead 4.6 43 –
Zinc – – –
FAAS SPE on soft husk of Pistachio Cadmium 0.13 133 – Sanaeepur et al. (2016)
Nickel 0.98 133 –
Lead 2.58 133 –
Zinc – – –
FAAS Multiwalled carbon nanotubes impregnated Cadmium 2.8 – 3.9 Saraji and Boroujeni (2014)
with 4-(2-thiazolylazo)resorcinol Nickel 4.3 – 4.6
Lead 7.2 – 1
Zinc 1.1 – 6.2
FAAS Fe3O4@SiO2@Isatin Cadmium 0.11 266 120 This work
Nickel 0.28 266 112
Lead 0.47 266 100
Zinc 0.21 266 100
a
Preconcentration factor
b
Maximum adsorption capacity

Acknowledgements Due to the support of this work, the author thanks
the Semnan University Research Council.
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